Addition agents for distillate fuel oils and stabilized distillate fuel oils containing the same



United States Patent ADDITION AGENTS FOR DISTILLATE FUEL OILS ANDSTABILIZED DISTILLATE FUEL OILS CON- TAINING THE SAME Elizabeth L.Fareri, Pittsburgh, and John P. Pellegrini,

Jr., Blawnox, Pa., assignors to Gulf Research & Development Company,Pittsburgh, Pa., a corporation of Delaware N0 Drawing. Filed Aug. 12,1954, Ser. No. 449,491

7 Claims. (Cl. 260-4675) This invention relates to addition agents fordistillate fuel oils and stabilized distillate fuel oils containing thesame. More particularly, the invention is concerned with thestabilization of distillate fuel oils containing a mixture of straightrun and catalytically cracked fuel oil distillates by incorporationtherein of the herein dis- 7 closed novel adducts.

Distillate fuel oil compositions containing mixed straight run andcatalytically cracked fuel oil distillates have proved exceptionally.troublesome with regard to sludge deposition during storage at normalatmospheric temperatures. It has been found that the sludgingcharacteristics of such mixed, or blended, fuel oil distillates arestrikingly poor, much poorer than can be accounted for from the knownsludging characteristics of the individual component fuel oildistillates alone. Although the exact cause for the unusual instabilityof mixed distillate fuel oils is not fully understood, the unusualcharacter and the unexpectedly large volume of sludge formed by suchmixed distillate fuel oils have led those skilled in the art to regardthe problem of sludge deposition in mixed distillate fuel oils asseparate and distinct from that of sludging or solids deposition inother oils.

More particularly, straight run distillate fuel oils containpredominantly paraifinic components. Sludge deposition in these oils,where such occurs, is considered to result from the presence of minoramounts of components that are not normally present and which impartinstability to the otherwise stable oil, e.g., impurities picked upduring refining, rather than from the inherent instability of thehydrocarbon components of the oil.

'The problem of sludge formation in such oils is con- :sideredessentially one involving oxidation and the formation of insolubleoxygenated products.

catalytically cracked fuel oil distillates on the other hand are rich inolefinic, aromatic and mixed olefinicaromatic compounds. Sludging insuch oils is considered to involve primarily condensation and/orpolymerization type reactions which result in the formation of insolublereaction products of relatively high molecular weight.

Still further, sludge deposition in blends of straight run andcatalytically cracked fuel oil distillates is an entirely distinctproblem from that for either component oil. While the sludge formed insuch blended fuel oils very probably contains some sludge of the typeformed in each component oil, the sludge formed in blended fuel oils isconsistently greatly in excess of the amount that can be accounted forfrom the known sludging tendencies of the individual component oils,thus indicating the existence of a special problem.

The problem of sludge deposition in mixed straight run and catalyticallycracked fuel oil distillates is not only distinct from that of sludgedeposition in individual fuel oil distillates, but also from that ofsludge deposition in lubricating oils and from that of gum formation ingasolines. In the former instance sludge formation is attributed to thehigh temperature oxidation of the highly parafiinic components containedin the oil, the reaction of acidic oxygenated products with metalscontacted therewith, and, in the case of crankcase lubricants, sludgeformation'is additionally attributed to the presence of foreignmaterials such as water, dust particles, carbon, incompletely burnedfuel and the like.

Gum formation in gasolines on the other hand is attributed primarily tothe oxidation of olefinic linkages (as opposed to oxidation ofparaflinic compounds); Moreover, the gums formed in gasoline are notnormally insoluble in the gasoline as is the case with sludge; instead,deposition of gums from gasoline occurs upon vaporization of the latter,rather than during storage as is the case with blended fuel oils.

We have found that sludge deposition in mixed catalytically cracked andstraight run fuel oil distillates can be substantially diminished byincorporation therein of small amounts of the novel adducts of thisinvention. The adducts included by this invention are the reactionproducts formed by the substantially spontaneous reaction of a phenoliccompound and a 1,3-diaminopropane having the following general formula:

where R is an aliphatic radical containing from 8 to 30 carbon atoms,and where the mol ratio of reactants is from about 0.5 to about 1 mol ofthe 1,3-diaminopropane per equivalent weight of phenolic compound. The

invention not only includes, the novel adducts themselves but alsostable distillate fuel oil compositions containing the same. i

The adducts of this invention are prepared by reaction of a phenoliccompound with a 1,3-diaminopropane that contains a long-chain aliphaticradical-substituted, secondary amino grouping. The aforesaid reactiontakes place substantially spontaneously at room temperature. In mostcases evolution of heat is observed, but in some cases the reaction hasbeen observed to occur with the adsorption of heat. Although even theendothermic reactions take place spontaneously at room temperature, inthe case of strongly endothermic reactions, or in the case .of highlyviscous reactants, the reaction may be caused to take placesubstantially spontaneously with the application of moderate heat. Theterm substantially spontaneously as used herein is meant to include notonly spontaneous reactions but also those in which moderate heating isutilized to accelerate and/or insure completion of the reaction. Subjectto the foregoing qualification, and provided that the decompositiontemperatures of the reactants and the reaction products are notexceeded, the reaction may be carried out at any temperature betweenabout 10 and about C. In order to produce the desired reaction products,the ratio of the reactants in the reaction mixture should be from about0.5 to about 1 mol of the 1,-3-diaminopropane per equivalent weight ofphenolic compound. The terms mol and equivalent weight are used intheir. conventional sense herein. Thus, the term mol is used to denote agram-molecular weight, while the term equivalent weigh as applied to thephenolic compounds, is used to denote that amount that would furnish onegram-ionic weight of hydrogen ion, if the compound were completelyionized. By way of example, an equivalent weight of phenol is equal tothe gram-molecular weight of phenol; an. equivalent weight of catecholis equal to one-half the gram-molecular weight of catechol.

'I'he diaminopropanes that form reaction products inwhere R is analiphatic radical containing from 8 to 30 carbon atoms. Thus, thepresent invention includes, for example, phenolic adducts of long-chainalkyl-, alkeriyland alkadienylaminopropylamines. Specific examples ofsuch diamino compounds are 3-octylaminopropylamine, 3decylaminopropylamine, 3 tetradecylaminopropylamine,3-tetradecenylaminopropylamine, 3-eicosylaminopropylarnine,3-eicosenylaminopropylamine, 3-docosyla- 'ininopropylamine, 3docosenylaminopropylamine, 3-docosodienylaminopropylamine, and3-triacontanylaminopropylamine. Within the general class of1,3-diaminopropanes capable of forming the adducts of this invention,'the diamines in which the long-chain, aliphatic N-sub- 'sti-tuent ofthe secondary amino grouping is an alkyl or hlkfe nyl group containingat least 12, and preferably from 1-2 to 18 straight chain carbon atomsare considered to ram especially effective addition agents. Examples ofl-,-3-diaminopropanes which are considered to form especially effectiveaddition agents for the purposes of this invention are the 3-dodecylandthe 3-hexadecylaminopropylamines, and especially the 18 carbonalkylalken- 3 1-, and alka-dienyl-substituted 1,3-diaminopropanes, suchas the 3-octadecy1-, 3-octadeeenyl-(3-oleyl-), and3-octadecadienylaminopropylamines. Although aliphatic hydrocarbonN-substituted 1,3-diaminopropanes are preterred, the invention includesphenolic reaction products "derived from diamines in which theN-substituent of the secondary amino grouping is itself substituted withone or more groups that contain elements such as oxygen, sulfur,nitrogen, phosphorus or halogen and that do not interfere with theoil-solubility of the adduct. Representative examples of1,3-diaminopropanes containing such substituents are3-ricinoleylaminopropylamine and 3- "(chlorostearyDaminopropylamine.Mixtures of 1,3-di- "'aminopropanes, such as are formed whenthelong-chain,

aliphatic N-substituent in the secondary amino grouping is derived frommixed fatty acids obtained from naturallysoccurring fats and oils, formhighly effective phenolic *adduct's Within the scope of this invention.In such instancesthe aliphatic N-substituent in the secondary amino:grouping will be a straight-chain, monovalent hydrocarbon radicalcontaining from 8 to 20 carbon atoms. Ex- "amples of such mixtures of1,3-diaminopropanm are 3-tallow'-aminopropylamine, 3 soyaaminopropylamine, and 3-coco-aminopropylamine, where therespective'N-substituents are mixed alkyl and unsaturated alkyl groupsderived from animal tallow (C -C fattyacids,

fsoybean (C -C fatty acids, and coconut (C -C iatty acids.

The phenolic compounds that form adducts with the -herein disclosedN-substituted 1,3-diaminopropanes in- "-butylphenol, 3,5-diethylphenol,3-ethyl-5-propylphenol,

m propylph enol, m butylphenol, m amylphenol, and p-octy1phenol,bis-(2-hydroxy-3,5 diamylphenyl)sulfide, mono-, his, andtris-alpha-methylbenzylphenols, alphaphenylethylcatechols, variousbis-(hydroxyalkylphenyl)- alkanes, representative of which are2,2-bis-(4-hydroxy- S-meth'ylphenyDpropane, 1, 1-bis-(2-hydroxy-3,5-dimethy1pheny1)isobutane, bis-.(2-hydroxy-3-t-butyl 5methylphenyl)methane, and 1,1-bis-(2-hydroxy-3 t butyl-S-methylphenyl)ethane. Although phenolic compounds in which the phenolicnucleus is substituted with hydrocarbon substituents are preferred, theinvention also includes the use of phenols containing non-hydrocarbonsubstituents-suchas nitro,-chloro, bromo, aminoand like groups, specificexamples of such phenols being -pnitfo phenol, p-amino phenol, andpentachloro :phenol. Commercial mixtures of phenols are also suitablefor the purposes of this invention. Such mixtures may be those recoveredby treatment of'industrial wastes, by treatment of petroleum refineryprocess waters, or from coal tar distillation or the like. 7

Although the exact nature of the adducts herein described has not beendefinitely ascertained, it is thought likely that these adducts partakeof the nature of substituted ammonium salts. Examples are given below ofthe formulae structure thought to be involved.

(c) H R At (a) is shown the probable formula for the reaction product ofequimolar proportions of a diamine and a monohydric phenolic compound.At (b) is shown the probable formula for the reaction product of 0.5 moldiamine with 1 mol of mo'nohydric phenolic compound. At (c) is shown theprobable formula for the reaction product of equimolar proportions of adiamine and a dihydric phenolic compound. In these formulae XO--represents the negative ion 'of'a monohydric phenol,

EXAMPLE I Approximately 7.5 grams (0.05 combining gram-molecular weight)of mixed m-alkyl phenols were admixed and reacted with 20.0 grams (0.05combining gram-molecular weight) of 3-tallow"-aminopropylamine. Thereaction occurred spontaneously and was complete in less than aboutfifteen minutes. A temperature change in the reaction mixture of from 29to 35 C. was noted during the course of thereaction. To insurecompletion of the reaction the mixture was heated to C., after nofurther spontaneous temperature rise was apparent. The

mixed m-alkyl phenols employed contained predominantly monoanddi-m-alkyl phenols in which the alkyl substituents contained not morethan 4'carbon atoms each, andi'n which the total alkyl-carbonatoms'was'between 3 and 5, together with substantial proportions of 4-and S-indanol. The mixture contained approximately 95'percent phenols.More particularly, in addition to indanols, the mixed phenols of thisexample contained m-alkyl phenols such as: 3-methyl-5-ethylpheno1,3-methyl-5-propylphenol, 3-methyl-5-butylphenol, 3,5-diethylphenol,3-ethyl-5-propylpheno1, m-propylphenol, m-butylphenol, and m-amylphenol.A sample of the mixed phenols had the following approximate make-up:

Percent by weight 4-indanol S-indanol 15 3-methyl-5-ethylphenol 10n-Propylphenols (meta and para) 5-10 Mixed meta-substituted phenols oftype indicated- 45-50 Apparent specific gravity at /20 C 1.03 Boilingrange (ASTM D-850):

I.B.P 240 C.

D.P 280 C. Vapor pressure at 20 C 0.01 mm. Hg. Viscosity at 20 C Approx.70 cps. Solubility in water at 20 C 0.08% by wt. Solubility of water in20 C 5% by wt. Refractive index at C 1.543 Behavior on cooling, sets toglass or clouds below C. Average weight per gal. at 60 F 8.63 lb. Flashpoint (open cup) 250 F.

The 3-tallow"-aminopropylamine employed in this example containedapproximately 80 percent diamines and was made up of a mixture of3-fatty alkyland alkenylaminopropylamines. The mixture had a theoreticalmolecular weight of 320, a combining weight of approximately 400, and amelting range of approximately 44 to 48 C. The fatty alkyl and alkenylsubstituents of the mixed diamines were derived from animal tallow fattyacids. Accordingly, the 3-"tallow"-aminopropylamine containedpredominantly 3-oley1aminopropylamine (3- octadecenylaminopropylamine),together with lesser proportions of 3-hexadecyland3-octadecylaminopropylamines, and small amounts of 3-myristyl-and3-linoleylaminopropylamines.

The adduct prepared according to the foregoing procedure was abrown-colored liquid material having the fol lowing analysis: Nitrogen,percent, 5.64.

EXAMPLE II The adduct formed by reaction of mxed malkyl phenols and3-tallow-aminopropylamine in the ratio of 0.5 mol diamine per equivalentweight of phenols (1:2 mol ratio) was prepared by reacting 15.0 grams(0.1

combining gram-molecular weight) of the mixed m-alkyl phenols describedin Example I with 20 grams (0.05 combining gram-molecular weight) of the3-tallow-aminopropylamine defined in Example I.

analysis: Nitrogen, percent, 4.57.

EXAMPLE III The reaction product formed by reacting the 3-tallow- WTPQPQ P P pil i l with mbfed i admixing 11.6 grams (0.05 combininggram-molecular,

weight) mixed alpha-methylbenzylphenols and 20.0 grams (0.05 combininggram-molecular weight) of 3- tallow-aminopropylamine. Again the reactionproceeded spontaneously, the temperature changing during the course ofthe reaction (less than 15 minutes) from 27 to 35 C. The mixture wasthen heated to 110 C.

The mixed alpha-methylbenzylphenols employed in the reaction were anapproximately percent pure mixture of substituted phenols containingpredominantly ortho- (alpha-methylbenzyl)phenol,bis-(alpha-methylbenzyD- phenol, and tris(alpha-methylbenzyl)phenol inthe respective approximate weight proportions of 12 percent, 2 percentand 36.7 percent, the balance of the over-all mixture being made up ofhigher substituted phenols.

The reaction product resulting from the foregoing re action was abrown-colored liquid material having the following analysis: Nitrogen,percent, 5.49.

EXAMPLE IV Another adduct was formed by reacting the3-tallowaminopropylamine of Example I with bis-(2-hydroxy-3,5-diamylphenyl)sulfide in a ratio of 1 mol of diamine per equivalentweight of the bis-phenol sulfide (2:1 mol ratio). The reaction wascarried out by admixing 20.0 grams (0.05 combining gram-molecularweight) of 3- tallow-aminopropylamine with 12.5 grams (0.025 combininggram-molecular weight) of the bis-phenol sulfide.

The materials reacted spontaneously, .a temperature change of 25 to 35C. being observed. When no further temperature change occurred, themixture was heated to C.

The product of the foregoing reaction was a viscous, brown-coloredliquid material having the following analysis:

Nitrogen, percent Sulfur, percent EXAMPLE V Another adduct was preparedby reacting 3-tallowaminopropylamine and para-octylphenol in a ratio of1 mol of diamine per equivalent Weight of phenol (1:1 mol ratio).According to this example 8.0 grams (0.02 combining gram-molecularweight) of the 3-"ta1low-aminopropylamine of Example I were admixed with4.13 grams (0.02 mols) of p-octylphenol. The temperature of the reactionmixture changed from 25 to 29 C. during the reaction, which proceededspontaneously. The mixture was heated to 110. C. after no furtherspontaneous temperature change was noted, in order to insure completionof the reaction. The product of the reaction was a tan-colored liquidmaterial having the following analysis: Nitrogen, percent, 5.61.

EXAMPLE VI A further adduct was formed by reacting3-laurylaminopropylamine and mixed m-alkyl phenols in a ratio of 1 molof diamine per equivalent weight of m-alkyl phenols (1:1 mol ratio). Inthis example 6.06 grams (0.02 mol) of 3-laurylaminopropylamine wereadmixed with 3.00 grams 0.02 combining gram-molecular weight) of themixed m-alkyl phenols of Example I. The materials reacted spontaneously,a temperature change of 28 to 20 C. being noted. At the conclusion ofthe spontaneous reaction period, the mixture was heated to 110 C. toinsure driving the reaction to completion. The product of the foregoingreaction was a brown-colored liquid material having the followinganalysis: Nitrogen,

percent, 7.68.

EXAMPLE VH An additional adduct was prepared by reacting 3 -(2-ethylhexyDaminopropylamine and mixed m-alkyl phenols in matte of 1 n'oier amine p'e'r equivalent weight or pheridls (1:1 e101 ratio). In'this reaction 9.32 grams (0505 non of 3-"(2ethylhexyl)amiriopropylarriine were admixed with "-7.50 grams (0.05combining gram-molecu- Iar "weight') of the mixed -'m-alkyl phenolsreferred to in Example I. The reaction proceeded spontaneously, atem'perature change of from 26 to 48C. being noted, with heat to 100 C.being added thereafter. The product of this reaction was a brown-coloredliquid material having the following analysis: Nitrogen, percent, 8.96.

EXAMPLE VIII "In'thisexainple 9.32 grams (0.05 mol) of3-(2-ethylhexyDaminopropylamine were admixed with 15.00 grams (0.1combining 'gfam rnolecular Weight) of the mixed 'r'n-alkyl phenolsdescribed in Example I. The ratio of reactant'was 0. 5 mol 'diamine 'perequivalent weight of phenols ('1:2 mol ratio). The materials reactedspont ane'oiisly, a temperature change of from 26 to 53 C. being noted.-The reaction mixture was then heated to 100 C. The product-of thisreaction was a browncolored liquid material having the followinganalysis: "Nifiogil, percent, 6.32.

The foregoing examples indicate the manner and ease "of preparation ofthe adducts of'this invention, and also described specific embodimentsof said adducts. Other adducts included by'th'e invention can beprepared similarly as "above by reaction in the indicated proportions"o'fother herein disclosed 1,3-diaminopropanes with the foregoingphenols, or with other members of the herein dis'closed class ofphenols. V V

The addition of very small amounts of the reaction products of theabove-described type to blended distillate fuel oils containing bothstraight run and catalytieauy cracked components has been found toprovide a niarked improvement in the sludging tendencies of the oils.Naturally, the various adducts of the herein disclosed class do notpossess exactly identical efiective- ;-ne s s, and the most advantageousconcentration for each such adduct will depend to some extent upon theparticular adduct used. Also, the minimum effective inhibitorconcentration may vary somewhat according to the specific nature of themixed fuel oil. In general, however, theherein disclosed reactionproducts are useful in concentrations of as little as about 0.005percent to about 1.0 percent by weight of the composition. Majorimprovement of the sludging characteristics of mixed fuel oils 'isusually obtainable by incorporation therein of from about 0.01 to about0.05 percent by weight of the heroin disclosed class of reactionproducts. Nevertheless, in some cases 'it'may be advantageous to add asmuch as about 0.1 percent by weight of the adducts. In veryunusual casesit'may be found desirable to add as much as about 1.0 percent by weightof the adducts.

The addition agents included by this invention may be incorporated inthe mixed fuel oils in any suitable manner. Thus, the adducts may beformed in situ in the oil, they may be added, per se, directly to themixed fuel oil, or they may be added in the form of concentrates, eitherimmediately after formation of the mixture of distillate'fuel oils, orafter the mixture has been stored'for a substantial period of time.Alternatively, the. sludge inhibiting addition agents of this inventionmay be-formed in situ in, or added per se or in the form of'concentratedsolutions to, either the straight run or thecatalyticallycracked fuel oil distillate, prior to blending of the components to forma mixed fuel oil. Suitable concentrates containing thesludge inhibitingadducts of this invention comprise, for example, 'mineral oil solutionsor dispersions containing'from about to 75 percent, and'prefe'rably fromabout to 50 percent, active ingredient. Where the concentrate is in theform of a dispersion, it may be desirable to heat the dispersion and/orthe oil that is to be inhibited, e.g., to a temperatiife' lbe'tween 100-F. -a'-nd140 '-F., in order to facilitate blending. alter-irate practiceinvolves blending at storage temperatures, utilizing concentratedsolutions of "the "additives in solvents that have a high solubility for'the additives and that do "not adversely affect the stabilityo'f theoil. Examples of such concentrated solutions are 10 to Weight percent,e.g., 50 percent, solutions of the reaction product of equimolar propor--tions of 3-tallow"-aminopropylamine and p-octylphenol in solvents suchas kerosene, benzene, toluene, hexane, methyl isobutyl ketone, andmethyl ethyl ketone.

As indicated, the class of distillate fuel oils to which this inventionis applicable includes mixtures of straight -run and catalyticallycracked distillate fuel oils such as are" used for domestic heating andfor some industrial heating purposes, typical of which are the so-calledNo. 2 fuel oils, i.e., distillate oils boiling within the range of about350 to 750 F. and having a minimum API gravity of about 26.

The problem of stabilization of such oils is unique and exists only whena catalytically cracked fuel oil distillate and a straight run fuel oildistillate are combined in suchproportions, as to cause a substantialdeleterious effect of the kind previously described. The invention isimportant when the ratio of the volume of the catalytically cracked tothe straight run oil-is 'within the range'of about 9:1 and about 1:9. Itis especially advantageous when applied to mixed oils containing theseoils in a volume ratio within the range of 4:1 and 1:4.

The utility of the herein disclosed class of sludge 'inhibiting adductsof long-chain, aliphatic N-substituted 1,3-diaminopropanes and phenolshas been demonstrated by. subjecting samples of a blend of catalyticallycracked and straight run fuel oil distillates containing various-concentrations of adducts representative of the class included by theinvention to astandard accelerated stability-test. The test samples weremade up by adding the desired concentration of each addition agent to betested directly to separate samples of the blended fuel oil which hadthe following physical properties:

Gravity, API... 33.5 Viscosity, SUS, 'F 34.5 Color, NPA 2 1.5+ Pourpoint, F --15 Flash point, F 168 Carbon residue, Conradson, on 10%bottoms---" 0.38 Neutralization value, acid No 0.12 Distillation Initialboiling point, F 360 End boiling point, F 630 Bromine No 11.7 Olefins,weight percent 15.1 Aromatics, volume percent 21.9 Aniline point, F 129Ash, oxide, weight percent 0.01

The stability test referred to was carried out on the mixed fuel oilcompositions by heating 600 gram samples of the fuel oil compositionsfor periods ranging from 16 to'64 hours at 210 F. in loosely stoppered,one-quart clear glass bottles. Following the heating periods the testsamplesiwere cooled to room temperature and filtered by suction throughtared, medium porosity fritted glass Goooh-type crucibles. The sludge ineach crucible was washed with heptane, Complete removal of the sludgeadhering to the inside of the bottles was obtained by means of a rubberpoliceman and heptane. The respec 'tive crucibles were dried in an ovenmaintained at 210 F. for 1 hour, cooled in a desiccator and reweighed.The increase in weight was recorded as milligrams of sludge per'600grams of oil.

As illustrating the improvement obtainable with the class of additionagents included by this invention the specific results obtained bytesting mixed fuel oil compositions containing the reaction productsdescribed in Examples I to V1, inclusive, are serfor'thinTable A.

Table A I Sludge, Mg./600 G. Oil

After After After Alter After 16 24 40 48 64 Hrs. Hrs. Hrs. Hrs. Hrs.

1. Blend A-lzlzl (Vol) Blend of West Texas Straight Run, South LouisianaStraight Run, and Fluid Oatalytically Cracked No. 2 Fuel Oil Distillate8.3 30. 2 69. 6 81. 2 99. 6 2. Blend A plus 0.02 Wt Percent ReactionProduct of Mixed Alkylpheno and low-aminopropylamine, 1:1 Mol Ratio(Example I Product) 2.3 0. 9 0. 4 0.7 0. 4 3. Blend A plus 0.05 Wt.Percent Reaction Product of Mixed Alkylphenols andB-Tallow"-aminopropylamine, 1:1 Mol Ratio (Example I Product) 2.0 4.Blend A plus 0.02 Wt. Percent Reaction Product of Mixed Alkylphenols and3-Tallow-aminopropylamine, 2:1 M01 Ratio (Example II Product) 1. 7 1. 23. 1. 7 0. 2 l5. Blend A plus 0.05 Wt. Percent Reaction Product of MixedAlkylphenols and 3-Tallow"-aminopropylamine, 2:1 Mol Ratio (Example IIProduct) 3. 2 6. Blend A plus 0.02 Wt. Percent Reaction Product of Mixeda-Methylbenzyl henols' and 8- Tallow"-aminopropylamine, 1:1 M01 Ratio(Example III Product 0. 6 7. Blend A plus 0.02 Wt. Percent ReactionProduct of Bis-(Z-hydro -3,5-diamylhegybsulfide and3-"Tallow"-aminopropylamine, 1:2 Mol Ratio Example IV 0 r0 uc 8. Blend Aplus 0.02 Wt. Percent Reaction Product of p Octylphenol andlowaminopropylamine, 1:1 Moi Ratio (Example V Product) 3. 3 9 Blend Aplus 0.02 Wt. Percent Reaction Product of Mixed Alkylphenols and3-Laury1aminopropylamine, 1:1 Mol Ratio (Example VI Product). 0.4

Compositions 2 to 9, inclusive, in the foregoing table are specificembodiments of the invention. Comparison of the results set forth in thetable for these compositions with those obtained for blank composition 1indicates the major improvement obtainable with the addition agentsincluded by this invention. The foregoing results are considered typicalof the preferred additives of this invention. Similar results areobtainable with other reaction products of the herein disclosed class,specific examples of which are the reaction products of3-dodecylaminopropylamine, 3-tetradecylaminopropylamine,S-hexadecylaminopropylamine, 3-octadecylaminopropylam-ine, and3-oct-adeceny-laminopropylamine with phenol, catechol, resorcinol,hydroquinone, cresol, bis (2 hydroxy 3 t butyl- S-methylphenyDmcthane,1,1 bis (2 hydroxy 3 tbutyl 5 methylphenyl) ethane, 3 methyl 5propylphenol, 3 methyl 5 butylphenol, 3,5 diethylphenol,S-ethyl-S-propylphenol, m-propylphenol, m-butylphenol, and m-amylphenol,in ratios of 0.5 and 1 mol of diamiue per equivalent weight of phenol.Other specific examples of addition agents included by the invention arereaction products of the foregoing phenols in the ratios indicated withmixed fatty alkyland alkenylaminopropylaminesa such as3-coco"-aminopropylamine and 3-soya-am inopropylamine. Other examples offuel oil compositions ineluded by the invention are mixtures ofcatalytically cracked and straight run No. 2 fuel oil distillates, wherethe volume ratio of cracked to straight run oil is from 9 1 to 1:9,e.g., 4:1, 2:1, 1:1, 1:2, 1:4, containing from 0.005 to 1.0 weightpercent, e.g., 0.01, 0.02, 0.03, 0.04, 0.05 percent, of the above-namedreaction products In order to demonstrate the importance of the use ofthe heroin disclosed class of 1,3-diaminopropanes in forming thereaction products of this invention, the results obtained byincorporating the reaction products of Examples VII and VIII in theblended fuel oil have been compared in Table B below with the resultsobtained by incorporation in the same fuel oil of a reaction product Inthe foregoing table, compositions 2 and 3 are specific embodiments ofthe invention. As indicated by the results obtained with thesecompositions and set forth in the foregoing table, reaction productsinvolving the use of C aliphatic N-substituted aminoproplaminesrepresent the threshold of utility insofar as sludge inhibition in mixedcatalytically cracked and straight run distillate fuel oils isconcerned. V

If desired, the stable fuel oil compositions of this invention maycontain in addition to the additives disclosed herein other improvementagents, such as for example, oxidation inhibitors, flash point controlagents, corrosion inhibitors, anti-foam agents, ignition qualityimprovers, combustion improvers and other additives adapted to improvethe oils in one or more respects.

Although, as indicated in the preliminary discussion of the problem ofsludging in blended fuel oils in relation to the problem ofdeterioration of other petroleum oils, the former is entirely distinct,the multifunctional reaction products of the herein disclosed inventionhave also been found to have utility in approximately the sameconcentrations that are used in fuel oils in inhibiting gum formation ingasolines. The utility of the herein disclosed reaction products ingasoline was determined by subjecting samples of a gasoline consistingof thermally cracked distillate to standard oxidation stability testASTM D525-49. According to this test the gasoline sample is introducedinto an oxidation bomb and oxygen is added to a pressure of about 100p.s.i. The charged bomb is placed in a boiling water bath and the gaspressure in the bomb is recorded. The end of the induction period, i.e.,the point at which rapid absorption of the oxygen by the gasoline takesplace, is the time when a sharp drop in pressure (at least 2 p.s.i. in15 minutes) occurs.

The results obtained by the foregoing test are indicated in Table Cbelow:

prepared by reaction of a' low molecular weight alkyl- 60 Table 6substituted aminopropylamine and a phenol. Addm C n T bl B tr a tioriGen Induction After 24 hrs. Miimtes 1. Blend A (see Table A) 30.2 66 1ia 2. Blend A plus 0.02 wt. percent reaction product of mixedalkylphenols and 3"(2'ethy1hexyl) 1 Blank Gasoline-Thermally Crackedaminopropylamine, 1:1 mol ratio, (Example Distillate 94 VII 27 2. Blankplus 2,4,6-Trl-tbutylphenol... 0.0525 0.0002 240 3. Blank plus ReactionProduct of 3. Blend A plus 0.02 wt. percent reaction product of 70Example I 0.1100 0. 0002 411 mixed alkylphenols and 3-(2-ethylhexyl)amifig gg Ream Pmdmt 0 1400 0 0002 479 nopropylamine, 2:1 mol ratio,(example VIII)- 28.1

4. Blend A plus 0.02 wt. percent reaction product ofbis-(2-hydroxy-3,5-diamylphenyl)sulfide and 3-isopropylaminopropylaminc, 1:2 mol ratio 64.8

in blended fuel oils were demonstrated by subjecting an other sample ofthe above-identified gasoline and asample' of a 50/50 by volume blend ofEastern Venezuela straight run and fluid catalytically cracked No. 2fuel oil distillates having a marked tendency to deposit sludge,respectively, to ASTM test 13525-49. instance a marked. drop in theoxygen pressure of the bomb was observed after only 97 minutes. stanceof the blended fuel .oil no marked. drop in the oxygen pressure hadoccurred after 161.5 hours, at which time the test was discontinued.

It will be apparentto those skilled in the art that many variations ofthe invention'rnay be resorted to without departing from the spiritthereof. Accordingly, only suchlimitations should be imposed as areindicated in the claims appended hereto.

1.'The reaction product formed -by' the substantially "spontaneousreaction of a phenolic compound that will not hinder'the-oil-solubilityof'said reaction'product and that is selected from the group consistingof unsubstituted and =mono-, 'di-, and trisubstituted monoand 'dihydricp h'enols whosesubstituents are selected 'fro'mthe group consisting of:alkyland 'aryl substituted radicals Icon- Ita-ini'n'g 1 -to 9carbonatoms, and 1 oil-soluble bisphenolic sulfides andaalkanesrlerived fromsuch phenols, and a 1, 3 diaminopropaneiof the general formula:

where R is an "aliphatic hydrocarbon radical selected from the' groupconsisting of alkyl, alkenyl, and alkadienyl containing from 8 to 30car-bon atoms, the "ratio of're- =actants-being'from'about 0.5to.abo'ut-1 mol"of the 1,3- =dian1inopropane per equivalent weight ofphenolic "compound.

In the former In the in- For example, the dissimilar natures of"3-alkyland 3-alkenylaminopropylamines Whose alkyl and alkenylsubstituents contain from 14 to 18 carbon atoms, the mol ratio ofreactants being from about 1 to 2 mols of phenols per mol ofamino-propylamines.

4. The mixed homologous reaction products formed-by the substantiallyspontaneous reaction of about equimolar proportions of mixedalpha-methylbenzylphenols and mixed 3-alkyland3-alkenylarninopropylamines whose alkyland alkenyl substituents containfrom 14 to 18 carbon atoms. 7

5. The mixed homologous reaction products formed by the substantiallyspontaneous reaction of bis-('Z-hydtoxy- 3,5-diamylphenyl)sulfide andmixed 3-alky1- and 3-alkenylaminopropylamines Whose alkyl and alkenylsubstitu- -'ents contain .from 14 to 18 carbon atoms, the-mol ratio ofreactants being about 1:2.

6. Thetmixed homologous reaction'products.formediby .the substantiallyspontaneous. reaction .of about equimol-ar .proportions of:p-octylph'enol and mixed 3-'alkyland 3 alkenylaminopropylamines whosealkyl and alkenyl substituents contain from 14m 18 carbon atoms.

7. The mixed homologous reaction products .forrned by the substantiallyspontaneousreaction of about equimolar proportions of3-laurylaminopropylamine and mixed m-alkyl'phenols whose alkylsubstituents containnot more than 4-carbon atoms each and whose totalalkyl .carbon atomssper molecule is from 3 to 5.

References Cited in the file of this patent UNITED STATES PATENTS2,048,770 Ayres July 23, L936 2,053,466 Downing et al Sept. 8, .19362,256,753 Scheumann Sept..23, 194:1 2,362,464 Britton et a1 a- Nov.14,119.44 2,385,848 :Smith et 'al Oct.'2, .1945 2,526,892 Minich Oct..24, v.1950 .2 ,68'4,292 Caron .et .al. .July 2.0, .1954

1. THE REACTION PRODUCT FORMED BY THE SUBSTANTIALLY SPONTANEOUS REACTIONOF A PHENOLIC COMPOUND THAT WILL NOT HINDER THE OIL-SOLUBILITY OF SAIDREACTION PRODUCT AND THAT IS SELECTED FROM THE GROUP CONSISTING OFUNSUBSTITUTED AND MONO-, DI-, AND TRISUBSTITUTED MONO- AND DIHYDRICPHENOLS WHOSE SUBSTITUENTS ARE SELECTED FROM THE GROUP CONSISTING OFALKYL AND ARYL-SUBSTITUTED RADICALS CONTAINING 1 TO 9 CARBON ATOMS, ANDOIL-SOLUBLE BISPHENOLIC SULFIDES AND ALKANES DERIVED FROM SUCH PHENOLS,AND A 1,3-DIAMINOPROPANE OF THE GENERAL FORMULA: